Enzymatic asymmetric hydroxylation of unnatural substrates with soybean lipoxygenase

Surrogate substrates mimicking the natural substrate (linoleic acid) bearin g a spacing prosthetic group with a non-ionic hydroxyl terminus undergo asy mmetric hydroxylation with soybean lipoxygenase. The prosthetic modifier su pplies the missing structural features needed for enzymatic recognition and controls the regiochemical outcome of the reaction by its high hydrophobic content. The effect of pH on the regiochemistry clearly shows that all the substrates can arrange themselves at the active site of soybean lipoxygena se in only one orientation leading to formation of hydroperoxides by oxygen ation at the omega -6 carbon. (C) 2001 Published by Elsevier Science Ltd.